EP0933362B1 - Procédé pour la préparation des dérivés de pyridine dicarboxylates - Google Patents

Procédé pour la préparation des dérivés de pyridine dicarboxylates Download PDF

Info

Publication number
EP0933362B1
EP0933362B1 EP99300409A EP99300409A EP0933362B1 EP 0933362 B1 EP0933362 B1 EP 0933362B1 EP 99300409 A EP99300409 A EP 99300409A EP 99300409 A EP99300409 A EP 99300409A EP 0933362 B1 EP0933362 B1 EP 0933362B1
Authority
EP
European Patent Office
Prior art keywords
formula
process according
pyridine
alkyl
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99300409A
Other languages
German (de)
English (en)
Other versions
EP0933362A1 (fr
Inventor
Robert Francis Doehner Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0933362A1 publication Critical patent/EP0933362A1/fr
Application granted granted Critical
Publication of EP0933362B1 publication Critical patent/EP0933362B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen

Definitions

  • Pyridine-2,3-dicarboxylc acids and esters are building blocks for numerous bio-active products, particularly imidazolinone herbicides, for example U.S. 4,758,667.
  • Known methods to prepare pyridine-2,3-dicarboxylate derivatives via the oxidation of a suitable quinoline or alkylpyridine precursor are often plagued by the use of costly oxidants such as KMnO 4 , H 2 Cr 2 O 7 , SeO 2 and the like; by long reaction time cycles such as in the use of ozone, electrolysis and the like; and by undesirable side reactions such as decarboxylation, N-oxide formation and the like. Therefore, new methods to construct the desired pyridine dicarboxylate product are continually being sought.
  • the present invention provides an efficient and effective process for the preparation of pyridine-2,3-dicarboxylate derivatives of formula I wherein
  • pyridine-2,3-dicarboxylate derivatives of formula I may be effectively prepared in a single vessel via the sequential condensation of a suitable alkyl vinyl ether of formula II with Vilsmeier reagent, an oxalacetate of formula III and an ammonia source.
  • X ⁇ represents Cl ⁇ or PO 2 Cl 2 ⁇ .
  • an alkyl vinyl ether of formula II which may be the cis isomer or the trans isomer or a mixture thereof, may be reacted with at least one molar equivalent of Vilsmeier reagent optionally in the presence of a first solvent to form a first intermediate (a vinylogous imidate salt), which may then be reacted with at least one molar equivalent of an oxalacetate of formula III in the presence of at least two molar equivalents of a base, preferably an organic amine base, to form a second intermediate(an iminium salt), which may be reacted with an ammonia source optionally (and preferably) in the presence of a second solvent to form the desired formula I pyridine-2,3-dicarboxylate product.
  • a first intermediate a vinylogous imidate salt
  • an oxalacetate of formula III in the presence of at least two molar equivalents of a base, preferably an organic amine base
  • Vilsmeier reagent designates the in situ product of the reaction of dimethyl formamide with an activating agent such as oxalyl chloride, phosgene, phosphorous oxychloride, thionyl chloride, and the like and may be illustrated as an immonium salt of formula IV or the analogues thereof wherein X ⁇ represents Cl ⁇ or PO 2 Cl 2 ⁇ .
  • halogen as used in the specification and claims designates Cl, Br, I or F.
  • Solvents suitable for use as the first solvent in the inventive process may be any inert organic solvent such as a hydrocarbon, e.g. hexanes, pentanes, heptanes and the like; a halogenated hydrocarbon, e.g. methylene chloride, chloroform, dichloroethane, and the like, preferably dichloroethane or methylene chloride; an aromatic hydrocarbon, e.g. benzene, toluene, xylene and the like; a halogenated aromatic hydrocarbon, e.g. chlorobenzene, o-dichlorobenzene, or mixtures thereof.
  • the reaction is conducted with a first solvent and preferably the first solvent is a halogenated hydrocarbon such as dichloroethane or methylene chloride.
  • Bases suitable for use in the inventive process are organic amines such as triethylamine, pyridine, lutidine, N,N-dimethylpiperidine, N-methylpyrrolidine and the like, preferably triethylamine or pyridine.
  • Ammonia sources suitable for use in the process of the invention may be any of the conventional means for producing NH 3 in situ, including ammonia gas, ammonium salts, and the like, preferably ammonium salts such as ammonium acetate, ammonium sulfamate, and the like.
  • Solvents suitable for use as the second solvent in the inventive process are protic solvents such as water; alcohols such as C 1 -C 4 alkanols e.g. ethanol, methanol, propanol, butanol and the like, preferably ethanol; organic acids such as C 1 -C 4 carboxylic acids e.g. acetic acid, propionic acid and the like, preferably acetic acid.
  • protic solvents such as water
  • alcohols such as C 1 -C 4 alkanols e.g. ethanol, methanol, propanol, butanol and the like, preferably ethanol
  • organic acids such as C 1 -C 4 carboxylic acids e.g. acetic acid, propionic acid and the like, preferably acetic acid.
  • the rate of formation of the reaction product is generally directly related to the reaction temperature. In general, lower temperatures will decrease the rate of reaction and higher temperatures will increase the rate of reaction. However, excessively high temperatures are not desired and may lead to a decrease in product yield and purity. Preferable temperatures range from about O°C to 120°C.
  • NMR nuclear magnetic resonance
  • a soution of dimethyl formamide (73 g, 1.00 mole) in ethylene dichloride is slowly treated with oxalyl chloride (88 mL, 1.00 mole), with cooling, stirred at ambient temperatures for 16 hours, treated with ethyl vinyl ether (72.1 g, 1.00 mole) over a 1 hour period and stirred at ambient temperatures for 16 hours.
  • This reaction mixture is treated sequentially with diethyl oxalacetate (199.28 g, 1.06 mole) and (with cooling) triethylamine (224 g, 2.2 mole), stirred for 0.5 hours and treated with a premixed solution of concentrated HCl (200 ml) and concentrated NH 4 OH (200 ml) in 100 ml of water.
  • the reaction mixture is treated further with water (250 ml), concentrated NH 4 OH (70 ml) and acetic acid (200 ml).
  • the resultant mixture is distilled under N 2 at 88°C and atmosphere pressure to remove 1850 g of distillate.
  • the distillation pot is then treated with absolute ethanol (1.0 L) and NH 4 OCOCH 3 (180 g), heated at reflux temperature for 16 hours and distilled at 100°C to remove 887 g of distillate.
  • the distillation pot is cooled and the residue is partitioned between water and 2:1 ethyl acetate/hexanes. The organic phase is separated, washed sequentially with water and brine and concentrated in vacuo to give the title product as an oil, 179.5 g, (77% pure) 58.5% yield, identified by NMR analysis.
  • the derivatives of formula I obtained by the process of this invention may be converted to herbicidal 2-(imidazolin-2-yl)-3-pyridine carboxylic acids by procedures described in US Patent No 4758667.
  • a 2,3-pyridine of formula I may be reacted in the presence of a strong base with an 2-aminoalkane carboxamide of formula V NH 2 -CR 4 R 5 CONH 2 wherein R 4 and R 5 are each independently C 1 -C 4 alkyl to give after pH adjustment a 2-(imidazolin-2-yl)-3-pyridine of formula:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Peptides Or Proteins (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (10)

  1. Procédé pour la préparation d'un composé de formule I
    Figure 00160001
    dans laquelle
       R1 est H ou un groupe alkyle en C1-C4 facultativement substitué par un groupe alcoxy en C1-C4 ou un halogène ; et
       R2 et R3 sont chacun indépendamment un groupe alkyle en C1-C6, qui comprend
    a) la réaction d'un éther d'alkyle et de vinyle de formule II
    Figure 00160002
    dans laquelle le composé de formule II est l'isomère cis, l'isomère trans, ou un mélange d'entre eux, R est un groupe alkyle en C1-C4 et R1 est tel que défini pour la formule I, avec au moins un équivalent molaire de réactif de Vilsmeier facultativement en présence d'un premier solvant pour former un premier intermédiaire ;
    b) la réaction dudit premier intermédiaire avec au moins un équivalent molaire d'un oxalacétate de formule III
    Figure 00160003
    dans laquelle R2 et R3 sont tels que définis pour la formule I, en présence d'au moins deux équivalents molaires d'une base du type amine organique pour former un second intermédiaire ; et
    c) la réaction dudit second intermédiaire avec une source d'ammoniac, facultativement en présence d'un second solvant, pour former le pyridine-diester de formule I comme produit.
  2. Procédé selon la revendication 1, dans lequel le premier solvant est présent et est un hydrocarbure halogéné.
  3. Procédé selon la revendication 1 ou la revendication 2, dans lequel la base est la triéthylamine.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le second solvant est présent et est un alcanol en C1-C4 ou un acide carboxylique en C1-C4 ou un mélange d'entre eux.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel la source d'ammoniac est l'acétate d'ammonium.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel R1 est H, un groupe méthyle, éthyle ou méthoxyméthyle.
  7. Procédé selon la revendication 6, dans lequel R1 est H.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel R3 et R4 sont chacun indépendamment un groupe méthyle ou éthyle.
  9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel les températures sont de préférence comprises entre environ 0°C à 120°C.
  10. Procédé pour préparer une 2-(imidazoline-2-yl)-3-pyridine de formule VI
    Figure 00180001
    en faisant réagir une 2,3-pyridine de formule I avec un 2-aminoalcane-carboxamide de formule V H2N-CR4R5CONH2 dans laquelle R4 et R5 sont chacun indépendamment un groupe alkyle en C1-C4, en présence d'une base forte et en ajustant le pH pour obtenir un composé de formule (VI), caractérisé en ce que la 2,3-pyridine de formule I est préparée par un procédé selon l'une quelconque des revendications 1 à 9.
EP99300409A 1998-01-28 1999-01-20 Procédé pour la préparation des dérivés de pyridine dicarboxylates Expired - Lifetime EP0933362B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/014,546 US5892050A (en) 1998-01-28 1998-01-28 Process for the preparation of pyridine dicarboxylate derivatives
US14546 1998-01-28

Publications (2)

Publication Number Publication Date
EP0933362A1 EP0933362A1 (fr) 1999-08-04
EP0933362B1 true EP0933362B1 (fr) 2002-04-03

Family

ID=21766102

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99300409A Expired - Lifetime EP0933362B1 (fr) 1998-01-28 1999-01-20 Procédé pour la préparation des dérivés de pyridine dicarboxylates

Country Status (23)

Country Link
US (1) US5892050A (fr)
EP (1) EP0933362B1 (fr)
JP (1) JP4346141B2 (fr)
KR (1) KR100566502B1 (fr)
CN (1) CN1118455C (fr)
AR (1) AR014500A1 (fr)
AT (1) ATE215533T1 (fr)
AU (1) AU756604B2 (fr)
BR (1) BR9900179B1 (fr)
CA (1) CA2260469C (fr)
CZ (1) CZ295307B6 (fr)
DE (1) DE69901130T2 (fr)
DK (1) DK0933362T3 (fr)
ES (1) ES2175899T3 (fr)
HU (1) HUP9900194A1 (fr)
IL (1) IL127853A (fr)
NZ (1) NZ333916A (fr)
PL (1) PL190302B1 (fr)
PT (1) PT933362E (fr)
SG (1) SG74697A1 (fr)
SK (1) SK283297B6 (fr)
TW (1) TW466234B (fr)
ZA (1) ZA99615B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010054952A1 (fr) * 2008-11-13 2010-05-20 Basf Se Acides 2-[(1-cyanopropyl)carbamoyl]-5-chlorométhylnicotiniques et leur utilisation dans la fabrication d'imidazolinones herbicides

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7032119B2 (en) * 2000-09-27 2006-04-18 Amphus, Inc. Dynamic power and workload management for multi-server system
EP2365965B1 (fr) 2008-11-13 2019-01-09 Basf Se Procédé de préparation de bromures de 3-pyridylméthylammonium substitués
JP5669744B2 (ja) * 2008-11-13 2015-02-12 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ５−クロロメチル−２，３−ピリジンジカルボン酸無水物の製造方法
TWI506019B (zh) 2008-12-08 2015-11-01 Basf Se 製造經取代５－甲氧基甲基吡啶－２，３－二羧酸衍生物之方法
EP2982673B1 (fr) 2008-12-09 2018-02-21 Basf Se Procédé de fabrication d'anhydride de 5-chloromethyl-pyridine-2,3-dicarboxylique
CN103724257B (zh) * 2012-10-11 2015-06-10 中国中化股份有限公司 一种制备2,3-二羧酸酯吡啶类化合物的方法
CN104447527B (zh) * 2013-09-23 2017-06-06 中国中化股份有限公司 一种制备吡啶‑2，3‑二羧酸酯化合物的方法
CN107759516B (zh) * 2016-08-16 2021-04-27 沈阳化工研究院有限公司 一种烷基醚取代吡啶-2，3-二羧酸衍生物的制备方法
EP3782985A1 (fr) 2019-08-19 2021-02-24 BASF Agrochemical Products B.V. Procédé de fabrication de dérivés d'acide 5-méthoxyméthylpyridine-2,3-dicarboxylique

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4656283A (en) * 1982-05-25 1987-04-07 American Cyanamid Company Alkyl esters of substituted 2-methyl-3-quinolinecarboxylic acid and quinoline-2,3-dicarboxylic acid
US5252538A (en) * 1984-05-21 1993-10-12 American Cyanamid Company (2-imidazolin-2-yl) fused heteropyridine compounds, intermediates for the preparation of and use of said compounds as herbicidal agents
US4723011A (en) * 1985-10-28 1988-02-02 American Cyanamid Company Preparation of substituted and disubstituted-pyridine-2,3-dicarboxylate esters
ATE82279T1 (de) * 1986-02-10 1992-11-15 Ciba Geigy Ag Verfahren zur herstellung von 2-(imidazolin-2-yl)-pyridin- und -chinolin-3-carbonsaeuren.
JPS62207238A (ja) * 1986-03-07 1987-09-11 Mitsubishi Paper Mills Ltd β−アルコキシアクロレイン誘導体の製造法
EP0296109A3 (fr) * 1987-06-18 1989-12-20 Ciba-Geigy Ag Dérivés de l'acide nicotinique -2(imidazolin-2-yl)
DE4025076A1 (de) * 1990-08-08 1992-02-13 Hoechst Ag Verfahren zur herstellung von estern der 5-alkylpyridin-2,3-dicarbonsaeure
DE19501478A1 (de) * 1995-01-19 1996-07-25 Bayer Ag Verfahren zur Herstellung von in 5-Stellung substituierten 2-Chlorpyridinen
US5925764A (en) * 1998-06-15 1999-07-20 Wu; Wen-Xue Process and intermediated for the manufacture of pyridine-2, 3-dicarboxylate compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010054952A1 (fr) * 2008-11-13 2010-05-20 Basf Se Acides 2-[(1-cyanopropyl)carbamoyl]-5-chlorométhylnicotiniques et leur utilisation dans la fabrication d'imidazolinones herbicides

Also Published As

Publication number Publication date
BR9900179B1 (pt) 2010-02-09
PL331068A1 (en) 1999-08-02
CN1118455C (zh) 2003-08-20
PL190302B1 (pl) 2005-11-30
DE69901130T2 (de) 2002-08-29
CA2260469C (fr) 2008-11-25
IL127853A0 (en) 1999-10-28
KR100566502B1 (ko) 2006-03-31
JP4346141B2 (ja) 2009-10-21
CZ295307B6 (cs) 2005-07-13
NZ333916A (en) 1999-07-29
DE69901130D1 (de) 2002-05-08
IL127853A (en) 2003-04-10
SG74697A1 (en) 2000-08-22
JPH11255749A (ja) 1999-09-21
CA2260469A1 (fr) 1999-07-28
BR9900179A (pt) 2000-05-09
ZA99615B (en) 2000-07-27
US5892050A (en) 1999-04-06
CN1227222A (zh) 1999-09-01
PT933362E (pt) 2002-09-30
HUP9900194A1 (hu) 2000-03-28
ES2175899T3 (es) 2002-11-16
AR014500A1 (es) 2001-02-28
CZ23499A3 (cs) 1999-08-11
TW466234B (en) 2001-12-01
EP0933362A1 (fr) 1999-08-04
KR19990068247A (ko) 1999-08-25
HU9900194D0 (en) 1999-03-29
SK10699A3 (en) 1999-08-06
AU756604B2 (en) 2003-01-16
SK283297B6 (sk) 2003-05-02
DK0933362T3 (da) 2002-07-01
AU1423599A (en) 1999-08-19
ATE215533T1 (de) 2002-04-15

Similar Documents

Publication Publication Date Title
US4948896A (en) Process for preparing pyridine-2,3-dicarboxylic acid compounds
IE59324B1 (en) Preparation of substituted and disubstituted pyridine-2,3-dicarboxylate esters
EP0933362B1 (fr) Procédé pour la préparation des dérivés de pyridine dicarboxylates
US5124458A (en) Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate
EP0560019B1 (fr) Procédé de préparation de dialkyl-2,3-pyridine carboxylates et de leurs dérivés à partir d'une oxime alpha-bêta insaturée et d'un aminobutènedioate
US5225560A (en) Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate
EP0965589B1 (fr) Procédé et intermédiaires pour la préparation des dérivés de pyridine-2,3-dicarboxylates
US6114535A (en) Process and intermediates for the manufacture of pyridine-2,3-dicarboxylate compounds
EP0899262B1 (fr) Procédé pour la préparation des amides et des esters d'acides hétéroarylcarboxyliques
US6320053B1 (en) Preparation of heteroarylcarboxamides
US5106986A (en) Preparation of aminoethanol derivatives
AU765659B2 (en) Process for the preparation of acid chloride compounds
MXPA99000729A (en) Process for the preparation of pyridine dicarboxylate derivatives
JP3895786B2 (ja) クロロピリジニウムクロリド類及びその製造法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20000202

AKX Designation fees paid

Free format text: AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

17Q First examination report despatched

Effective date: 20001027

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF AKTIENGESELLSCHAFT

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

REF Corresponds to:

Ref document number: 215533

Country of ref document: AT

Date of ref document: 20020415

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69901130

Country of ref document: DE

Date of ref document: 20020508

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: SCHMAUDER & PARTNER AG PATENTANWALTSBUERO

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20020401828

Country of ref document: GR

ET Fr: translation filed
REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20020612

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2175899

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20030106

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20090114

Year of fee payment: 11

Ref country code: IE

Payment date: 20090115

Year of fee payment: 11

Ref country code: ES

Payment date: 20090218

Year of fee payment: 11

Ref country code: DK

Payment date: 20090113

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20090116

Year of fee payment: 11

Ref country code: NL

Payment date: 20090104

Year of fee payment: 11

Ref country code: FI

Payment date: 20090114

Year of fee payment: 11

Ref country code: DE

Payment date: 20090115

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20081215

Year of fee payment: 11

Ref country code: GB

Payment date: 20090114

Year of fee payment: 11

Ref country code: CH

Payment date: 20090114

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20090213

Year of fee payment: 11

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: SCHMAUDER & PARTNER AG PATENT- UND MARKENANWAELTE VSP;ZWAENGIWEG 7;8038 ZUERICH (CH)

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20090108

Year of fee payment: 11

Ref country code: IT

Payment date: 20090128

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20090113

Year of fee payment: 11

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20100720

BERE Be: lapsed

Owner name: *BASF A.G.

Effective date: 20100131

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20100801

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100120

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100930

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100801

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100131

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100201

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100120

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100803

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100720

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100120

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100120

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110321

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100121

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100120

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20150127

Year of fee payment: 17

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 215533

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160120